High zirconia fused cast refractory

ABSTRACT

To provide a high zirconia fused cast refractory having high durability, which hardly has cracks during the heating, by temperature changes during use and during the cooling at the time of suspension of operation. A high zirconia fused cast refractory which has a chemical composition comprising from 86 to 96 mass % of ZrO 2 , from 2.5 to 8.5 mass % of SiO 2 , from 0.4 to 3 mass % of Al 2 O 3 , from 0.4 to 1.8 mass % of K 2 O, at most 0.04 mass % of B 2 O 3 , at most 0.04 mass % of P 2 O 5  and at most 3.8 mass % of Cs 2 O and containing substantially no Na 2 O.

TECHNICAL FIELD

The present invention relates to a high zirconia fused cast refractory. Particularly, it relates to a high zirconia fused cast refractory having excellent durability and reusability even when applied to a glass melting furnace, and being excellent in the productivity.

BACKGROUND ART

Heretofore, a high zirconia fused cast refractory comprising at least 80 mass % of ZrO₂ as a chemical component has been used as a refractory for a glass melting furnace. A high zirconia fused cast refractory, which has high corrosion resistance against molten glass and low contamination properties, has been frequently used for a portion of contact with molten glass of a glass melting furnace for glass which is required to have high quality, such as substrate glass for a flat panel display.

The microstructure of a high zirconia fused cast refractory is composed of a slight quantity of pores, a large amount of zirconia (ZrO₂) crystal grains and a small amount of matrix glass with which the space between the grains is filled. This matrix glass contains SiO₂ as the main component and contains other oxides, such as Al₂O₃, Na₂O, B₂O₃ and P₂O₅.

A high zirconia fused cast refractory is exposed to temperature changes in cooling step at the time of its production, and during the heating in a glass melting furnace and during the cooling at the time of suspension of operation, by the process in operation and by corrosion of the refractory itself. By such temperature changes, a thermal stress, and a transformation stress caused by reversible transformation of zirconia crystals accompanied by a significant volume change in a temperature range in the vicinity of 1,000° C., occur in the interior of the refractory. When matrix glass having appropriate thermomechanical properties in an appropriate amount is contained in the refractory, the refractory is flexible against the above stresses, and the stresses are relaxed, whereby no cracks will form on the refractory.

Whereas, if the thermomechanical properties of the matrix glass are inappropriate or if the amount of the matrix glass is insufficient, cracks may form at the time of production of the high zirconia fused cast refractory or during the heating when the refractory is applied to a glass melting furnace. If the refractory has cracks when applied to a portion of contact with molten glass, this portion will be severely corroded by molten glass, whereby the durability of the refractory will significantly be decreased.

In the interior of a high zirconia fused cast refractory, zircon crystals (ZrO₂.SiO₂) may be formed in some cases. The zircon crystals in the interior of the refractory are formed by reaction of ZrO₂ and SiO₂ in the matrix glass, and accordingly formation of the zircon crystals leads to a decrease in the matrix glass in the refractory. Such a refractory in which zircon crystals are formed and the amount of the matrix glass which relaxes the thermal stress and the transformation stress is reduced becomes fragile and is likely to have cracks even by a slight temperature change.

Further, even in a high zirconia fused cast refractory in which zircon crystals are hardly formed by the refractory itself, zircon crystals may be formed by a reaction with molten glass in some cases. This is because one or both of elution of chemical components which suppress formation of zircon crystals in the refractory into molten glass, and invasion of chemical components which accelerate formation of zircon crystals into the refractory from molten glass, occurs. The tendency of the zircon crystals to be formed by the reaction with molten glass is remarkable when the refractory is in contact with low alkali glass such as liquid crystal substrate glass or with alkali-free glass.

Accordingly, in a case where a high zirconia fused cast refractory in which zircon crystals are likely to be formed by the thermal history by the refractory itself, or a high zirconia fused cast refractory in which zircon crystals are hardly formed by the refractory itself but zircon crystals are likely to be formed by a reaction with molten glass, is used as a refractory for a glass melting furnace, even when no cracks form at the time of production and even when no cracks form during the heating, zircon crystals may be formed in the interior of the refractory in operation, whereby cracks are likely to form by the temperature changes in operation, and the durability of the refractory is significantly decreased in some cases.

In general, the durability of the refractory is a factor which determines the life of a glass melting furnace. Accordingly, formation of cracks in the refractory shortens the life of a glass melting furnace, which is one cause to increase the cost for glass production.

Further, in a high zirconia fused cast refractory in which no zircon crystals are formed in a state where the glass meting furnace is in operation, no cracks will form, or even if cracks will form, they are few and small as compared with a refractory in which zircon crystals are formed, and formation of new cracks or propagation of existing cracks during the cooling when the operation of the glass melting furnace is suspended for e.g. adjustment of production tends to be little, and accordingly such a refractory is relatively easily reused.

On the other hand, in a high zirconia fused cast refractory in which zircon crystals are formed, formation of new cracks and propagation of existing cracks are remarkable during the cooling, and further, formation of cracks and propagation occur during the heating again, and thus reusing such a refractory is difficult. Even if it is reused, no high durability will be obtained, and the furnace life will be short That is, a high zirconia fused cast refractory in which zircon crystals are likely to be formed by itself or by a reaction with molten glass, even if it has a remaining life in a state where the glass melting furnace is in operation, is unsuitable for reuse after suspension of operation.

A means to suppress formation of cracks in a high zirconia fused cast refractory at the time of production, during the heating and in operation has been studied.

Patent Document 1 discloses a high zirconia fused cast refractory which has a chemical composition comprising from 85 to 97 mass % of ZrO₂, from 2 to 10 mass % of SiO₂, at most 3 mass % of Al₂O₃ and from 0.1 to 3 mass % of P₂O₅, and containing substantially no rare-earth oxide, whereby cracks to be formed at the time of production are suppressed. However, this refractory contains P₂O₅ which accelerates formation of zircon crystals, and has a drawback such that zircon crystals are likely to be formed even by the refractory itself.

Patent Document 2 proposes a refractory which has a chemical composition comprising from 90 to 98 mass % of ZrO₂ and at most 1 mass % of Al₂O₃, containing no Li₂O, Na₂O, CuO, CaO and MgO, and containing from 0.5 to 1.5 mass % of B₂O₃, or containing from 0.5 to 1.5 mass % of B₂O₃ and containing at most 1.5 mass % of one member selected from K₂O, SrO, BaO, Rb₂O and Cs₂O or a total content of two or more of them of at most 1.5 mass %, whereby cracking at the time of production is suppressed, and the electrical resistivity is increased using an element component having a large cation radius. However, the refractory has a high content of B₂O₃ which accelerates formation of zircon crystals, and has a drawback such that zircon crystals are likely to be formed even by the refractory itself.

Patent Document 3 discloses a refractory which has a chemical composition comprising from 90 to 95 mass % of ZrO₂, from 3.5 to 7 mass % of SiO₂, from 1.2 to 3 mass % of Al₂O₃ and from 0.1 to 0.35 mass % in total of Na₂O and/or K₂O, and containing substantially no P₂O₅, B₂O₃ and CuO, whereby improvement in the heat cycle resistance and suppression of formation of zircon crystals are realized. However, even the refractory of this invention has an insufficient effect to suppress formation of zircon crystals under conditions of contact with molten glass.

Patent Document 4 proposes a refractory which has a chemical composition comprising from 89 to 96 mass % of ZrO₂, from 3.5 to 7 mass % of SiO₂, from 0.2 to 1.5 mass % of Al₂O₃, from 0.05 to 1.0 mass % of Na₂O+K₂O, less than 1.2 mass % of B₂O₃, less than 0.5 mass % of P₂O₅, higher than 0.01 mass % and less than 1.7 mass % of B₂O₃+P₂O₅, less than 0.3 mass % of CuO, at most 0.3 mass % of Fe₂O₃+TiO₂, from 0.01 to 0.5 mass % of BaO, and at most 0.3 mass % of SnO₂. Patent Document 4 discloses that cracking at the time of production of the refractory and cracking by the heat cycle will not occur, and further, addition of Na₂O, K₂O and BaO cause unfavorable properties of P₂O₅ and B₂O₃ which accelerate formation of zircon crystals, to disappear. However, even the refractory of this invention still has an insufficient effect to suppress formation of zircon crystals under conditions of contact with molten glass. The reasons are such that Na₂O is contained in the refractory in Examples of this invention, and by its remarkable effect to decrease the viscosity of the matrix glass, compositional displacement of the refractory and molten glass is accelerated, whereby substantial performance to suppress formation of zircon crystals is decreased, and that B₂O₃ and P₂O₅ having an effect to accelerate formation of zircon crystals are contained in a relatively high content.

Patent Document 5 discloses a refractory which has a chemical composition comprising from 87 to 94 mass % of ZrO₂, from 3.0 to 8.0 mass % of SiO₂, from 1.2 to 3.0 mass % of Al₂O₃, higher than 0.35 mass % and at most 1.0 mass % of Na₂O and higher than 0.02 mass % and less than 0.05 mass % of B₂O₃, containing substantially no P₂O₅ and CuO, and having a mass ratio of Al₂O₃ to Na₂O of from 2.5 to 5.0, whereby formation of zircon crystals by the refractory itself is suppressed. However, in this refractory based on this invention, formation of zircon crystals is suppressed by optimizing the content ratio of Na₂O and Al₂O₃, and accordingly under conditions of contact with molten glass containing Na₂O only in a low content, elution of Na₂O occurs in priority. The refractory has a drawback such that by such elution, the content ratio of Na₂O and Al₂O₃ will soon deviate from the initial value in an unused state, the composition of the refractory departs in a short time from a composition advantageous for suppression of formation of zircon crystals, and the effect to suppress formation of zircon crystals obtainable by the refractory itself is soon lost.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: JP-A-56-129675

Patent Document 2: JP-A-63-285173

Patent Document 3: JP-A-6-72766

Patent Document 4: JP-A-9-2870

Patent Document 5: JP-A-2007-176736

DISCLOSURE OF INVENTION Technical Problem

The present invention has been made to solve the above problems, and its object is to provide a high zirconia fused cast refractory which is less likely to have cracks at the time of production, during the heating, by temperature changes during use and the cooling at the time of suspension of operation, and is thereby have high durability.

Solution To Problem

The present inventor has conducted extensive studies and as a result, found a high zirconia fused cast refractory in which zircon crystals are hardly formed even under conditions of contact with molten glass even by the refractory itself, and has low residual volume expansion even under temperature cycle conditions.

That is, the high zirconia fused cast refractory of the present invention has a chemical composition comprising from 86 to 96 mass % of ZrO₂, from 2.5 to 8.5 mass % of SiO₂, from 0.4 to 3 mass % of Al₂O₃, from 0.4 to 1.8 mass % of K₂O, at most 0.04 mass % of B₂O₃, at most 0.04 mass % of P₂O₅ and at most 3.8 mass % of Cs₂O and containing substantially no Na₂O.

Advantageous Effects of Invention

The high zirconia fused cast refractory of the present invention is free from problems of cracking at the time of production of the refractory and is excellent in the productivity, in the refractory, zircon crystals are hardly formed even in contact with molten glass even by the refractory itself, the refractory hardly has cracks at the time of production of the refractory, during the heating, during use and during the cooling, and it its excellent in the durability and the reusability.

Further, the high zirconia fused cast refractory of the present invention hardly has cracks even under conditions of contact with molten glass and is excellent in the durability, and accordingly a long life of a furnace will be obtained even when it is applied to a portion of contact with molten glass of a glass melting furnace, the amount of corrosion of the refractory can be reduced, and contamination of molten glass can be reduced. Further, it hardly has cracks even during the cooling at the time of suspension of operation of the glass melting furnace by e.g. adjustment of production, and during the heating again, and accordingly it is possible to use the refractory which is less corroded and does not reach the end of its life. Further, the high zirconia fused cast refractory of the present invention is free from problems of cracking which influence the yield at the time of production, and accordingly it is excellent in the productivity of the refractory, and as a result, products can be produced relatively at a low cost.

DESCRIPTION OF EMBODIMENTS

The high zirconia fused cast refractory of the present invention (hereinafter sometimes referred to simply as a fused cast refractory or a refractory) comprises the above chemical components. The roles played by these respective components in the refractory will be described below. In the following description, three components of Na₂O, B₂O₃ and P₂O₃ are represented by outer percentage assuming that the total content of components other than the above three components to be 100 mass %. On the other hand, components other than the three components of Na₂O, B₂O₃ and P₂O₅ are represented by inner percentage.

In this specification, “inner percentage” is meant for the proportion of the component in 100 mass % when the entire fused cast refractory (excluding any component represented by outer percentage) is taken as 100 mass %. For example, “ZrO₂ is contained in an amount of 90 mass % in terms of inner percentage” means that when the entire fused cast refractory (excluding any component represented by outer percentage) is taken as 100 mass %, ZrO₂ is contained in an amount of 90 mass % in such 100 mass %.

On the other hand, “outer percentage” is a proportion, based on the entire fused cast refractory (excluding any component represented by outer percentage), of a component not included in 100 mass % when the entire fused cast refractory (excluding any component represented by outer percentage) is taken as 100 mass %. For example, “Na₂O is contained in an amount of 0.01 mass % in terms of outer percentage” means that when the entire refractory (excluding any component represented by outer percentage) is taken as 100 mass %, Na₂O is additionally contained in an amount of 0.01 mass %.

The zirconia raw material and the zircon raw material to be used for production of the high zirconia fused cast refractory inevitably contains from 1 to 3 mass % of HfO₂, and HfO₂ is not substantially lost e.g. by evaporation at the time of production and remains in the refractory, and accordingly, a usual high zirconia fused cast refractory including the refractory of the present invention contains from 1 to 3 mass % of HfO₂. Since HfO₂ usually plays the same role as ZrO₂ in a high zirconia fused cast refractory, a value for ZrO₂+HfO₂ is commonly represented simply as ZrO₂, and in the present invention also, a value for ZrO₂+HfO₂ is represented as ZrO₂.

The fused cast refractory of the present invention is a high zirconia fused cast refractory composed of a large amount of zirconia crystals, a small amount of matrix glass and a very small quantity of pores. ZrO₂ has a high resistance to corrosion by molten glass and is contained as a main component in the refractory. Most of this ZrO₂ is present as zirconia crystals having an excellent corrosion resistance to molten glass, and only very small amount of it is present in the matrix glass.

That is, the content of ZrO₂ dominates the content of zirconia crystals in the refractory of the present invention and thus influences the corrosion resistance of the refractory to molten glass. In order to obtain high corrosion resistance to molten glass, the ZrO₂ content is required to be at least 86 mass %, and is preferably at least 88 mass %. On the other hand, if the ZrO₂ content is higher than 96 mass %, the amount of the matrix glass which relaxes a stress is relatively small, and cracks are likely to form at the time of production, or by temperature changes during the heating, during use and during the cooling. Accordingly, the content of ZrO₂ in the refractory of the present invention is from 86 to 96 mass %.

SiO₂ is a main component to form the matrix glass. In order to ensure the amount of the matrix glass which functions to relax a stress, SiO₂ in an amount of at least 2.5 mass % is required. On the other hand, if a large amount of SiO₂ is contained in the refractory, as a matter of course, ZrO₂ cannot be contained in a large amount, and the corrosion resistance is lost. Accordingly, the content of SiO₂ in the refractory of the present invention is from 2.5 to 8.5 mass %, preferably from 3.0 to 8.0 mass %.

Al₂O₃ is a component to reduce the viscosity of the matrix glass and at the same time, a component to suppress formation of zircon crystals to a certain extent. Even under conditions of contact with low alkali glass or alkali-free glass under which formation of zircon crystals is remarkable, since many of such glasses have a relatively high content of Al₂O₃, the concentration gradient difference as between the refractory and molten glass is small, and elution of Al₂O₃ from the refractory is slow. Accordingly, the effect to suppress formation of zircon crystals by Al₂O₃ will last for a long period of time.

If the Al₂O₃ content is less than 0.4 mass %, the viscosity of the matrix glass tends to be too high, whereby the performance of the matrix glass to relax a stress will be lowered, and accordingly cracks are likely to form at the time of production, or by temperature changes during the heating, during use and during the cooling. On the other hand, if Al₂O₃ is contained in a high content, the viscosity of the matrix glass is lowered more than necessary, and elution of K₂O and Cs₂O which are effective to suppress formation of zircon crystals into molten glass is accelerated, such being disadvantageous. Further, if the Al₂O₃ content exceeds 3 mass %, aluminosilicate crystals such as mullite will be formed at the time of production or during use, whereby the amount of the matrix glass is reduced, and accordingly cracks are likely to form at the time of production, or by temperature changes during the heating, during use and during the cooling. Accordingly, the Al₂O₃ content in the refractory of the present invention is from 0.4 to 3 mass %, preferably from 0.5 to 2.7 mass %.

K₂O is also a component to reduce the viscosity of the matrix glass and at the same time, a component to suppress formation of zircon crystals. Like Al₂O₃, K₂O has a role to reduce the viscosity of the matrix glass, and by incorporating K₂O in the refractory, an effect to suppress cracking on the refractory at the time of production, or by temperature changes during the heating, during use and during the cooling will be obtained. Further, since the cation radius of K is large, elution of K₂O is slow even upon contact with molten glass, whereby an effect to suppress formation of zircon crystals will last over a long period of time.

If the amount of K₂O is insufficient, aluminosilicate crystals such as mullite are likely to be formed by heating at the time of production or during use, thus leading to a decrease in the amount of the matrix glass, whereby cracks are likely to form at the time of production, or by temperature changes during the temperature increase, during use and during the cooling. On the other hand, if K₂O is present in an amount of at least 1.8 mass %, potassium-containing aluminosilicate crystals such as leucite are likely to be formed by heating at the time of production or during use, thus leading to a decrease in the amount of the matrix glass, whereby cracks are likely to form at the time of production, or by temperature changes during the heating, during use and during the cooling. The effect to suppress formation of zircon crystals by the refractory itself can be obtained only with K₂O in a very slight amount, however, to suppress formation of zircon crystals under conditions of contact with molten glass, particularly under conditions of contact with low alkali glass or alkali-free glass, K₂O in an amount of at least 0.4 mass % is required. Accordingly, the content of K₂O in the refractory of the present invention is from 0.4 to 1.8 mass %, preferably from 0.5 to 1.5 mass %, further preferably from 0.6 to 1.2 mass %.

B₂O₃ is a component to accelerate formation of zircon crystals. If B₂O₃ is contained in a large amount, in the refractory, zircon crystals are formed only by the thermal history, and even with a small amount, formation of zircon crystals under conditions of contact with molten glass is accelerated in some cases. Accordingly, with a view to suppressing formation of zircon crystals, the content of B₂O₃ is preferably low. In the present invention in which Al₂O₃, K₂O and Cs₂O greatly contribute to suppression of formation of zircon crystals, a B₂O₃ content up to 0.04 mass % is accepted, and the content is preferably at most 0.03 mass %. The B₂O₃ content is more preferably at most 0.02 mass %.

On the other hand, B₂O₃ has an effect to suppress formation of cracks at the time of production of the refractory even in a low content, and accordingly B₂O₃ is contained in the refractory within a range not to impair suppression of formation of zircon crystals, and the composition is precisely controlled, to maintain high productivity of the refractory.

P₂O₅ is a component to accelerate formation of zircon crystals like B₂O₃. If P₂O₅ is contained in a large amount, in the refractory, zircon crystals are formed only by the thermal history, and even with a small amount, formation of zircon crystals under conditions of contact with molten glass is accelerated in some cases. Accordingly, with a view to suppressing formation of zircon crystals, the content of P₂O₅ is preferably as low as possible.

On the other hand, P₂O₅ has an effect to suppress formation of cracks at the time of production of the refractory even in a low content, and further, depending on the type of the zirconia raw material or the zircon raw material, it is a component which is inevitably included. In a case where inclusion of P₂O₅ is not accepted at all, a relatively expensive zircon raw material or zirconia raw material which is an expensive purified raw material or the production area of which is limited must be used. However, in the present invention in which Al₂O₃, K₂O and Cs₂O greatly contribute to suppression of formation of zircon crystals, a P₂O₅ content up to 0.04 mass % is accepted, and the P₂O₅ content is preferably at most 0.03 mass %. The P₂O₅ content is more preferably at most 0.02 mass %. Accordingly, the range from which the zircon raw material or the zirconia raw material is selected is not narrowed, and a relatively low raw material cost can be achieved. Further, in the same manner as in the case of B₂O₃, P₂O₅ may be contained in the refractory within a range not to impair suppression of formation of zircon crystals, and the composition is precisely contained, whereby high productivity of the refractory can be maintained.

Na₂O is a component having an effect to suppress formation of zircon crystals by the thermal history by the refractory itself, however, its effect is inferior to those of K₂O and Cs₂O under conditions of contact with molten glass, and is far inferior in a relatively low temperature range of less than 1,400° C. under conditions of contact with molten glass. Further, Na₂O is also a component to reduce the viscosity of the matrix glass like Al₂O₃ and K₂O, and its effect to reduce the viscosity is particularly remarkable, and it accelerates elution of Al₂O₃, K₂O and Cs₂O which are components effective to suppress formation of zircon crystals, into molten glass, and accelerates invasion of components which accelerate formation of zircon crystals such as B₂O₃, from molten glass under conditions of contact with molten glass.

Further, since the cation radius of Na is small, Na₂O will readily be eluted into molten glass upon contact with low alkali glass, alkali-free glass or the like, and accordingly when the refractory is in contact with such molten glass, the effect to suppress formation of zircon crystals will last only in a relatively short period of time. In addition, since the effect of the Na₂O to reduce the viscosity of the matrix glass is particularly remarkable, if Na₂O is contained in the refractory of the present invention containing Al₂O₃ and K₂O at a relatively high concentration, the viscosity of the matrix glass will excessively be reduced, whereby the shape-retention property at the time of production of the refractory is lowered, and deformation or cracking in the form of tears will form on an ingot, and accordingly the productivity of the refractory will remarkably be lowered.

Accordingly, the Na₂O content is preferably low, and in the present invention, substantially no Na₂O is contained. Here, “containing substantially no Na₂O” means that its content is at most 0.04 mass %. The Na₂O content is preferably at most 0.03 mass %, more preferably at most 0.02 mass %.

Further, in the present invention, in addition to the above-described components, Cs₂O may be contained. Cs₂O is a component to suppress formation of zircon crystals, and its effect appears even in a low content. Further, since the cation radius of Cs is very large, elution of Cs₂O from the refractory is extremely slow even upon contact with molten glass, and accordingly an effect to suppress formation of zircon crystals will last for a particularly long period of time. On the other hand, although the reason is not clearly understood, excess Cs₂O tends to cause cracks to form at the time of production, and accordingly the Cs₂O content is within a range of at most 3.8 mass %, preferably from 0.05 to 3.5 mass %, more preferably from 0.05 to 2.5 mass %, particularly preferably from 0.05 to 0.7 mass %.

Fe₂O₃ and TiO₂ which are contained mainly as impurities in the raw material (zircon raw material, zirconia raw material or the like) are components to cause coloring and blistering of molten glass, and a high content of them is unfavorable. When the total content of Fe₂O₃ and TiO₂ is at most 0.3 mass %, there will be no problem of coloring, and the total content is preferably not higher than 0.2 mass %.

Likewise, Y₂O₃ and CaO are contained as impurities in the raw material, and they tend to increase the rate of residual volume expansion in a heat cycle test. A total content of Y₂O₃ and CaO of at most 0.3 is not problematic, and the total content is preferably not higher than 0.2 mass %.

CuO is a component to cause coloring of molten glass even with a small amount, and accordingly only a content to such a level that substantially no coloring occurs is accepted. In the refractory of the present invention, the CuO content is preferably at most 0.02 mass %, more preferably at most 0.01 mass %.

EXAMPLES

Now, the high zirconia fused cast refractory of the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.

In order to obtain a high zirconia fused cast refractory by an electrically fusing and casting method, raw materials such as alumina, zircon sand, silica, potassium carbonate, cesium carbonate, B₂O₃ and P₂O₅ were blended to desilicated zircon as a zirconia raw material, to obtain mixed raw materials, and such mixed raw materials were introduced into a single phase arc electric furnace with an output power of 500 kVA equipped with two graphite electrodes and completely melted by Joule heating.

This melt was poured into a graphite mold having an internal volume of 160 mm×200 mm×350 mm preliminarily embedded in a Bayer alumina powder as an annealing material, cast and left to cool to a temperature in the vicinity of room temperature. After the cooling, the ingot and the graphite mold were taken out from the annealing material, and the graphite mold and the ingot were separated to produce the desired high zirconia fused cast refractory.

By adjusting the raw material compositions, high zirconia fused cast refractories having chemical compositions as identified in Tables 1 and 2 were obtained. Table 1 shows Examples of the present invention (Ex. 1 to 9) and Table 2 shows Comparative Examples (Ex. 10 to 18). With respect to the chemical composition of the refractory, values for ZrO₂, SiO₂ and Al₂O₃ are quantitatively analyzed values determined by a wavelength dispersive X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, apparatus name: ZSX Primus II), and values for the other components are quantitatively analyzed values determined by an inductively-coupled plasma emission spectrophotometer (manufactured by Seiko Instruments Inc., apparatus name: SPS 1100). However, quantitative determination for the respective components is not limited to such analysis methods, and can be carried out by another quantitative analysis method.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex.9 Compo- ZrO₂ 92.9 96.0 86.1 91.1 91.7 90.0 92.3 94.3 92.0 sition SiO₂ 4.7 2.5 8.5 6.4 6.5 5.4 5.7 3.9 6.5 of re- Al₂O₃ 0.8 0.6 0.6 0.4 0.8 3.0 0.9 0.7 0.8 fractory K₂O 0.7 0.5 1.1 1.8 0.4 0.8 0.7 0.8 0.4 (mass %) Na₂O Less than 0.02 0.04 Less than Less than Less than 0.04 0.04 0.01 0.01 0.01 0.01 0.01 B₂O₃ 0.03 0.01 0.03 0.04 Less than Less than Less than 0.01 0.04 0.01 0.01 0.01 P₂O₅ Less than 0.01 Less than 0.02 Less than Less than Less than 0.04 Less than 0.01 0.01 0.01 0.01 0.01 0.01 Cs₂O 0.7 Less than 3.5 0.1 0.3 0.6 0.1 0.1 Less than 0.1 0.1 Fe₂O₃ + TiO₂ 0.1 0.2 0.1 0.1 0.2 0.1 0.2 0.1 0.1 CaO + Y₂O₃ 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.2 Charac- Cracking at Nil Medium Medium Small Small Small Small Medium Nil teristics the time of production Rate of residual 1.5 2.8 1.4 2.0 1.2 1.4 1.8 2.8 1.7 volume expansion in heat cycle test (vol %) Rate of form- Less than Less than Less than Less than Less than Less than Less than Less than Less than ation of zircon 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 crystals in heat cycle test (mass %) Rate of form- Less than 1.3 Less than 0.7 2.4 1.2 1.4 2.4 3.8 ation of zircon 0.5 0.5 crystals in immersion test 1 (mass %) Rate of form- Less than 1.1 Less than 2.0 2.1 Less than 0.7 3.1 3.3 ation of zircon 0.5 0.5 0.5 crystals in immersion test 2 (mass %) Electrical 60 Not Not Not 76 Not Not Not 82 resistivity at measured measured measured measured measured measured 1,500° C. (Ω · cm)

TABLE 2 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Compo- ZrO₂ 96.9 91.8 88.6 90.9 89.1 91.2 91.3 93.3 90.5 sition SiO₂ 2.1 6.9 7.3 7.6 7.1 7.2 7.1 5.2 3.8 of re- Al₂O₃ 0.4 0.3 3.2 0.8 0.8 0.8 0.8 0.7 0.8 fractory K₂O 0.4 0.6 0.6 0.3 2.0 0.5 0.5 0.4 0.5 (mass %) Na₂O Less than Less than 0.03 Less than 0.02 0.09 0.15 0.05 Less than 0.01 0.01 0.01 0.01 B₂O₃ 0.02 0.08 Less than Less than 0.03 Less than 0.03 0.03 0.02 0.01 0.01 0.01 P₂O₅ 0.01 0.02 Less than Less than Less than Less than 0.07 Less than 0.01 0.01 0.01 0.01 0.01 Cs₂O Less than 0.1 0.1 0.1 0.7 Less than Less than 0.1 4.1 0.1 0.1 0.1 Fe₂O₃ + TiO₂ 0.1 0.1 0.1 0.2 0.2 0.1 0.2 0.1 0.1 CaO + Y₂O₃ 0.1 0.2 0.1 0.1 0.1 0.2 0.1 0.2 0.2 Charac- Cracking at Large Small Large Large Large Medium Large Nil Large teristics the time of production Rate of residual 4.5 2.2 3.3 1.8 3.9 1.7 1.4 11.4 6.4 volume expansion in heat cycle test (vol %) Rate of form- Less than Less than Less than Less than Less than Less than Less than 3.9 Less than ation of zircon 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 crystals in heat cycle test (mass %) Rate of form- 1.7 3.4 2.2 4.2 Less than 4.4 5.5 7.9 1.6 ation of zircon 0.5 crystals in immersion test 1 (mass %) Rate of form- 1.4 2.7 1.9 2.9 0.8 3.1 3.8 7.1 1.6 ation of zircon crystals in immersion test 2 (mass %) Electrical Not Not 71 87 Not Not Not Not Not resistivity at measured measured measured measured measured measured measured 1,500° C. (Ω · cm)

[Cracking at the Time of Production]

Presence or absence of cracks in an outer appearance of the ingot was evaluated as follows.

First, presence or absence of cracks was visually examined, and with respect to a refractory having cracks, the entire surface of the ingot was ground to a depth of 10 mm, and a case where the crack length in the ingot after grinding was at most 10 mm is rated as cracking at the time of production being “small”, a case where the crack length was longer than 10 mm and at most 50 mm was rated as cracking at the time of production being “medium”, and a case where the crack length was longer than 50 mm was rated as cracking at the time of production being “large”. In a case where a refractory has no cracks at the time of production, there will be no problem in production of the refractory. Further, in a case of cracking at the time of production being medium or smaller, such a refractory can easily be produced only by producing an ingot which is slightly larger than a refractory of a necessary size and moderately grinding the surface of such an ingot. On the other hand, in a case of cracks at the time of production being large, it is necessary to prepare a very large ingot relative to a refractory of a necessary size, and further to considerably grind or cut the ingot, and accordingly production of such a refractory costs very high and is not realistic.

[Rate of Residual Volume Expansion in Heat Cycle Test]

A 40 mm×40 mm×40 mm sample was cut out from a produced fused cast refractory, and subjected to repetition of heating and cooling between 800° C. and 1,250° C. for 40 times. On that occasion, heating from room temperature to 800° C. was carried out at a rate of 160° C. per hour, and from this point, heating to 1,250° C. at a rate of 450° C. per hour immediately after the temperature reached 800° C., and cooling to 800° C. at a rate of 450° C. per hour immediately after the temperature reached 1,250° C., were carried out for one heat cycle. The heat cycle between 800° C. and 1,250° C. was repeatedly carried out 40 times. After the final heat cycle, the sample was cooled from 800° C. to room temperature at a rate of 160° C. per hour. The dimensions of the sample were measured before and after the test, and the rate of residual volume expansion was determined from the change in the dimensions.

In this heat cycle test, a high zirconia fused cast refractory usually shows residual volume expansion, and in some cases, it has cracks. This residual volume expansion results from a test of a refractory by itself against heat cycles in a relatively low temperature region, and indicates, when the refractory is applied to a glass melting furnace, the cracking resistance in the vicinity of the furnace outer surface at a relatively low temperature away from the molten glass. The rate of residual volume expansion by this test is preferably less than 3 vol %, more preferably less than 2 vol %.

[Rate of Formation of Zircon Crystals in Heat Cycle Test]

Further, in some refractories, zircon crystals are formed by the heat cycle test. With respect to the fused cast refractory after subjected to the above heat cycle test, the rate of formation of zircon crystals was obtained by a powder X-ray diffractometer (manufactured by Rigaku Corporation, apparatus name: RINT-TTR Ill). That is, with respect to a powder obtained by grinding the sample after the heat cycle test, X-ray diffraction measurement was carried out, peak area ratios of zircon crystals and zirconia crystals were obtained from the resulting diffraction pattern, and the mass % of zircon crystals was determined by the ratio of zircon crystal amount/(zircon crystal amount +zirconia crystal amount).

[Rate of Formation of Zircon Crystals in Immersion Test]

The rate of formation of zircon crystals under conditions of contact with molten glass was obtained by the following immersion test. That is, a 15 mm×25 mm×30 mm sample was cut out from the obtained fused cast refractory, inserted into a 200 cc platinum crucible together with 250 g of alkali-free glass cullet, and heated at a predetermined temperature for a predetermined time in an electric furnace (manufactured by MOTOYAMA K.K., apparatus name: NH-2025D-SP). After cooling, the sample was taken out and ground. With respect to the ground sample powder, X-ray diffraction measurement was carried out, peak area ratios of zircon crystals and zirconia crystals were obtained from the resulting diffraction pattern, and the mass % of zircon crystals were determined from the ratio of zircon crystal amount/(zircon crystal amount +zirconia crystal amount), which was regarded as the rate of formation of zircon crystals.

Glass used for this test is alkali-free glass having a chemical composition comprising, as calculated as oxides, 60 mass % of SiO₂, 8 mass % of B₂O₃, 17 mass % of Al₂O₃, 3 mass % of MgO, 4 mass % of CaO and 8 mass % of SrO.

The test conditions in the immersion test were as follows.

As the immersion test 1, a test at 1,250° C. for 20 days was carried out. In this test, heating from room temperature to 1,250° C. was carried out at a rate of 300° C. per hour, and after the temperature reached 1,250° C., the temperature was maintained for 20 days, the temperature was decreased to 700° C. at a rate of 500° C. per hour and further decreased from 700° C. to room temperature at a rate of 60° C. per hour. In this test, the rate of formation of zircon crystals is preferably at most 4 mass %, more preferably at most 2 mass %.

As the immersion test 2, a test at 1,450° C. for 4 days was carried out. In this test, heating from room temperature to 1,450° C. was carried out at a rate of 300° C. per hour, and after the temperature reached 1,450° C., the temperature was maintained for 4 days, and then the temperature was decreased to 700° C. at a rate of 500° C. per hour and further decreased from 700° C. to room temperature at a rate of 60° C. per hour. In this test, the rate of formation of zircon crystals is preferably at most 4 mass %, more preferably at most 2 mass %.

[Electrical Resistivity at 1,500° C.]

The electrical resistivity was measured as follows. Firstly, a circular plate sample having a diameter of 20 mm and a thickness of from 3 to 5 mm was cut out from the fused cast refractory. On one side of the sample, a main electrode and a guard electrode were, and on the other side, only a main electrode was, printed with platinum paste. A platinum electrode to measure the electrical resistance of the sample was set in an electric furnace capable of raising the temperature to the maximum temperature of 1,700° C., and then the sample was introduced into the electric furnace. While heating at a temperature raising rate of 5° C./min, the volume resistance was continuously measured by a three-terminal method in accordance with JIS C2141 while applying an AC voltage (constant) with a frequency of 120 Hz by an insulation resistance meter (manufactured by ULVAC-RIKO, Inc., apparatus name: EHR-2000SP). From the obtained volume resistance, a volume resistivity was calculated and taken as the electrical resistivity in the present invention.

The above test results are shown in Tables 1 and 2.

As evident from Table 1, the fused cast refractories in the present invention had no cracks at the time of production, or even if they have, the crack size was medium or smaller. Accordingly, the fused cast refractory of the present invention can easily be produced with a high productivity.

Each of the fused cast refractories in Ex. 1 to 9 which are Examples of the present invention had a rate of residual volume expansion in the heat cycle test of less than 3 vol %. Further, although not shown in Table 1, each of samples in Examples of the present invention had no cracks formed in this test. It was found that the fused cast refractory of the present invention has a high cracking resistance against temperature changes by the refractory itself.

With respect to each of the fused cast refractories in Ex. 1 to 9, no zircon crystals were detected from the sample after the heat cycle test. According to this measurement method, zircon crystals can be detected when the rate of formation of zircon crystals is 0.5 mass % or higher. Thus, it can be said that in fused cast refractories in Ex. 1 to 9, substantially no reaction to form zircon crystals occurred in the heat cycle test. That is, in the fused cast refractory of the present invention, formation of zircon crystals by the refractory itself is suppressed.

With respect to the fused cast refractories in Ex. 1 to 9, the rate of formation of zircon crystals in the immersion test 1 was at most 4 mass %. Further, with respect to the fused cast refractories in Ex. 1 to 9, the rate of formation of zircon crystals in the immersion test 2 was also at most 4 mass %.

Since with respect to the refractories in Ex. 1 to 9, the rate of formation of zircon crystals was at most 4 mass % in both of the immersion test 1 and the immersion test 2, it can be said that in the fused cast refractory of the present invention, zircon crystals are hardly formed even under glass contact conditions.

That is, the refractory of the present invention is free from the problem of cracking at the time of production, it has a low rate of residual volume expansion by the heat cycles by the refractory itself, zircon crystals are hardly formed in it, and further, formation of zircon crystals in it is suppressed even under conditions of contact with molten glass, and accordingly, the refractory of the present invention is a highly durable refractory excellent in the productivity, durability against temperature changes during use and further reusability.

Especially, the refractory in Ex. 1 is free from cracking at the time of production, has a particularly low rate of residual volume expansion in the heat cycle test and has a particularly low rate of formation of zircon crystals in the glass immersion test, and accordingly, it is a fused cast refractory particularly excellent in the productivity, the cracking resistance against temperature changes during use and further reusability.

As shown by the electrical resistivities in Ex. 1, 5 and 9, the refractory of the present invention does not have a particularly high electrical resistivity, and has an electrical resistivity of a usual high zirconia fused cast refractory.

In Table 2, high zirconia fused cast refractories not corresponding to the present invention are shown as Comparative Examples.

In Ex. 10, 12, 13, 14, 16 and 18, cracking at the time of production were large respectively due to insufficient SiO₂, excess Al₂O₃, insufficient K₂O, excess K₂O, excess Na₂O, and excess Cs₂O, and in Ex. 16, cracking in the form of tears and deformation of the ingot were observed. Accordingly, it is very difficult to produce such refractories.

In Ex. 10, 12, 14, 17 and 18, the rate of residual volume expansion in the heat cycle test was 3 vol % or higher respectively due to insufficient SiO₂, excess Al₂O₃, excess K₂O, excess P₂O₅ and Na₂O, and excess Cs₂O, and it is found that these refractories are inferior in the cracking resistance against temperature changes by the refractories themselves.

In Ex. 17, a large amount of zircon crystals were formed by excess P₂O₅ in the heat cycle test, and the matrix glass was reduced, thus leading to a particularly high rate of residual volume expansion. In a refractory such as one in Example 17, zircon crystals are easily formed by the refractory itself, and when such a refractory is used in a glass melting furnace, the refractory will easily have cracks, and accordingly such a refractory cannot be expected to have high durability and is completely unsuitable for reuse.

In Ex. 11, 13, 16 and 17, the rate of formation of zircon crystals in the immersion test was high respectively due insufficient Al₂O₃ and excess B₂O₃, insufficient K₂O, excess Na₂O, and excess Na₂O and P₂O₅. In these refractories, suppression of formation of zircon crystals under conditions of contact with molten glass is insufficient

It is found from the above results that the high zirconia fused cast refractory of the present invention is excellent in the productivity, it hardly has cracks during the heating, zircon crystals are hardly formed in it even by the thermal history by the refractory itself, and zircon crystals are hardly formed in it even upon contact with molten glass. Accordingly, it is a high zirconia fused cast refractory which hardly has cracks even by temperature changes during use or during the cooling at the time of suspension of operation, which has high durability and which is also excellent in the reusability, and it is particularly suitable for a melting furnace for low alkali glass and alkali-free glass.

INDUSTRIAL APPLICABILITY

The high zirconia fused cast refractory of the present invention has high durability and favorable reusability, prolongs the life of a glass melting furnace, reduces glass defects, and makes it easy to suspend the operation of a glass melting furnace and restart it, and accordingly it is suitable particularly as a refractory for a glass melting furnace.

This application is a continuation of PCT Application PCT/JP2011/073014, filed on Oct. 5, 2011, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2010-227015 filed on Oct. 6, 2010. The contents of those applications are incorporated herein by reference in its entirety. 

What is claimed is:
 1. A high zirconia fused cast refractory which has a chemical composition comprising from 86 to 96 mass % of ZrO₂, from 2.5 to 8.5 mass % of SiO₂, from 0.4 to 3 mass % of Al₂O₃, from 0.4 to 1.8 mass % of K₂O, at most 0.04 mass % of B₂O₃, at most 0.04 mass % of P₂O₅ and at most 3.8 mass % of Cs₂O and containing substantially no Na₂O.
 2. The high zirconia fused cast refractory according to claim 1, which contains from 0.05 to 3.5 mass % of Cs₂O.
 3. The high zirconia fused cast refractory according to claim 2, which contains from 0.05 to 0.7 mass % of Cs₂O.
 4. The high zirconia fused cast refractory according to claim 1, wherein the content of Na₂O is at most 0.02 mass %.
 5. The high zirconia fused cast refractory according to claim 1, wherein the total content of Fe₂O₃ and TiO₂ is at most 0.3 mass %.
 6. The high zirconia fused cast refractory according to claim 1, wherein the total content of Y₂O₃ and CaO is at most 0.3 mass %.
 7. The high zirconia fused cast refractory according to claim 1, wherein the content of CuO is at most 0.02 mass %.
 8. The high zirconia fused cast refractory according to claim 1, which is for a glass melting furnace. 